CN102060528A - High Curie point and low lead piezoelectric ceramic material and preparation method thereof - Google Patents
High Curie point and low lead piezoelectric ceramic material and preparation method thereof Download PDFInfo
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- CN102060528A CN102060528A CN 201010563341 CN201010563341A CN102060528A CN 102060528 A CN102060528 A CN 102060528A CN 201010563341 CN201010563341 CN 201010563341 CN 201010563341 A CN201010563341 A CN 201010563341A CN 102060528 A CN102060528 A CN 102060528A
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Abstract
The invention relates to a high Curie point and low lead piezoelectric (PZT) ceramic material and a preparation method thereof, belonging to the technical field of the applications of the function ceramic. Bi is used to perform displacement modification on the PZT ceramic and a template grain growth method (TGG) is adopted to prepare the low lead PZT ceramic of which Curie temperature is improved. The chemical formula of the PZT ceramic is Bi(Zn1/2Ti1/2)O3-PbTiO3. The PZT ceramic can be widely used in numerous important scientific research and industrial departments such as aerospace, petrochemical engineering, metallurgy and geological exploration and in the high temperature accelerometer, the high temperature sensor, the vortex shedding flowmeter, the piezoelectric device of the bolt hole cold expanding technology and the like. The invention has the following effects: as Bi is used to replace partial Pb in the preparation process, the content of Pb in ceramic can be effectively reduced, the environmental coordination of the PZT ceramic can be increased, the Curie temperature of the material can be increased and the application range can be expanded.
Description
Technical field
The present invention relates to low lead piezoelectric ceramics material of a kind of high curie point and preparation method thereof, belong to the function ceramics applied technical field.
Background technology
Pb (Zr, Ti) O
3Base pottery (PZT) belongs to ABO
3The type perovskite structural material has excellent piezoelectric property, its Curie temperature height, and piezoelectricity is strong, and good stability has a wide range of applications in fields such as transmitter, piezoelectric transformer, ultrasonic transducer, resonator, ignition and blasting device, ultrasonic delay lines.But the preparation of PZT pottery needs a large amount of lead oxidess that contains, its production process and offal treatment stage all bring certain harm to environment, and along with science and technology development, the Curie-point temperature of PZT has been difficult to satisfy the demand in fields such as aerospace, petrochemical industry metallurgy.The particularly requirement in fields such as high temperature jerkmeter, pyrostat, vortex shedding flow meter.Therefore the low plumbous good high curie point piezoelectric ceramics of environment compatibility of exploitation is a problem with great realistic meaning.
PZT is ceramic modified to be the hot subject in piezoelectricity field always, and people such as USSR (Union of Soviet Socialist Republics) scientist G.A.Smlensky have studied A (B
1/2B '
1/2) O
3Type and A (B
1/3B '
2/3) O
3The composite perofskite type material, the elements compounding of discovery employing different valence state replaces A, the B position ion in the perovskite structure, not only can increase the degree of freedom of regulating the piezoelectric ceramics performance, and has greatly enriched the kind of piezoelectric ceramics.
The Bi sill is compared with the material of Pb base, and very strong piezoelectricity and very high polarization are arranged, and environmental harmony is also better.We can carry out the A position to PZT in view of the above and replace the B position, come modification to form new sosoloid, because Bi
3+With Pb
2+Have identical outer stable electrical minor structure, and Bi there are higher ionic valence condition and less ionic radius, the PbTiO that makes the Bi modification
3Series has more stable chemical bonding structure and stronger chemical b `, thereby makes the Curie temperature of total system be improved.
Summary of the invention
The objective of the invention is to utilize Bi and composite perofskite type compound (Ti, Zn etc.) to ABO
3The PbTiO of type perovskite structure
3In Pb carry out the part substituting modification, adopt template grain growth (TGG), with the SrTiO of sheet perovskite structure
3As mould material, comprehensive utilization crystal grain orienting technology, flow casting molding and isostatic cool pressing processing method prepare a kind of novel piezoceramic material with high-curie temperature.
The objective of the invention is to be achieved through the following technical solutions:
High curie point hangs down the lead piezoelectric ceramics preparation methods, is to adopt template grain growth (TGG), with the SrTiO of sheet perovskite structure
3As mould material, comprehensive utilization crystal grain orienting technology, flow casting molding and isostatic cool pressing processing method, concrete grammar is as follows:
1) adopts molten-salt growth method synthesizing flaky SrTiO
3Crystal is mainly finished by two steps, at first at 1150 ℃, and synthesizing flaky presoma Sr in the fusing assistant KCl/NaCl fused salt mixt
3Ti
2O
7, and then pass through SrTiO
3Growth unit is at the tabular crystal Sr of the first step acquisition
3Ti
2O
7On carry out growing and preparing and go out flaky SrTiO
3Crystal.
2) get the Bi of 500-800g
2O
3, TiO
2, ZnO, PbO, press Bi (Zn
1/2Ti
1/2) O
3-PbTiO
3Mixed carry out pre-burning together, stoichiometric ratio is 1: 3: 1: 2.
3) with the SrTiO that makes
3Template and BZT-PT powder are as the powder of preparation casting slurry, add solvent, dispersion agent, binding agent and plastic agent, prepared slurry is through curtain coating, the dry biscuit that obtains afterwards, the curtain coating biscuit is cut, carries out sintering after lamination, isostatic cool pressing and the plastic removal, obtain piezoceramic material.
Effect of the present invention is: substitute part Pb with Bi in preparation process, not only can effectively reduce the content of Pb in the pottery, increase the environment compatibility of piezoelectric ceramics, but also increased the Curie temperature of material, expanded its use range.Can be widely used in fields such as space flight, petrochemical industry, metallurgy, geological prospecting.
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
At 1150 ℃, synthetic 3h in the fusing assistant KCl/NaCl fused salt mixt, preparation sheet SrTiO
3Crystal.
Get 235gBi
2O
3, 120gTiO
2, 40.5gZnO, 245gPbO.Press Bi (Zn
1/2Ti
1/2) O
3-PbTiO
3Stoichiometric ratio mix and carry out pre-burning, temperature is 850 ℃ to 1000 ℃, wherein Bi is excessive 5%, Pb is excessive 10%, in order to the volatilization of Bi and Pb in the compensation sintering.
With the SrTiO that makes
3Template and BZT-PT powder are as the powder of preparation casting slurry, adding 300-350g ethanol is that dispersion agent, 60-70g polyvinyl butyral are that binding agent and 30-35g dibutyl phthalate are plastic agent as solvent, 12-15g triolein, prepared slurry is through obtaining biscuit after 600 μ m curtain coatings, 45 ℃ of dry 12h, with curtain coating biscuit 200MPa isostatic cool pressing 10min, carry out sintering after 500 ℃ of plastic removal 24h, obtain piezoelectric ceramics.
Embodiment 2
At 1150 ℃, synthetic 3h in the fusing assistant KCl/NaCl fused salt mixt, preparation sheet SrTiO
3Crystal.
Get 188gBi
2O
3, 96gTiO
2, 32.4gZnO, 196gPbO.Press Bi (Zn
1/2Ti
1/2) O
3-PbTiO
3Stoichiometric ratio mix and carry out pre-burning, temperature is 850 ℃ to 1000 ℃, wherein Bi is excessive 5%, Pb is excessive 10%, in order to the volatilization of Bi and Pb in the compensation sintering.
With the SrTiO that makes
3Template and BZT-PT powder are as the powder of preparation casting slurry, and adding 200g-300g ethanol and butanone mixed solvent is 2: 1 as solvent, ratio.The 8-12g triolein is that dispersion agent, 50-60g polyvinyl butyral are that binding agent and 20-30g dibutyl phthalate, polyoxyethylene glycol mixed solution are plastic agent, prepared slurry is through obtaining biscuit after 500 μ m curtain coatings, 45 ℃ of dry 12h, with curtain coating biscuit 200MPa isostatic cool pressing 10min, carry out sintering after 500 ℃ of plastic removal 24h, obtain piezoelectric ceramics.
Claims (3)
1. a high curie point hangs down the lead piezoelectric ceramics material, and its chemical formula is Bi (Zn
1/2Ti
1/2) O
3-PbTiO
3
2. the method for preparing the low lead piezoelectric ceramics material of high curie point as claimed in claim 1, this method are to adopt template grain growth, with the SrTiO of sheet perovskite structure
3As mould material, comprehensive utilization crystal grain orienting technology, flow casting molding and isostatic cool pressing processing method, concrete grammar is as follows:
(1) adopts molten-salt growth method synthesizing flaky SrTiO
3Crystal is mainly finished by two steps, at first at 1150 ℃, and synthesizing flaky presoma Sr in the fusing assistant KCl/NaCl fused salt mixt
3Ti
2O
7, and then pass through SrTiO
3Growth unit is at the tabular crystal Sr of the first step acquisition
3Ti
2O
7On carry out growing and preparing and go out flaky SrTiO
3Crystal;
(2) get the Bi of 500-800g
2O
3, TiO
2, ZnO, PbO, press Bi (Zn
1/2Ti
1/2) O
3-PbTiO
3Mixed carry out pre-burning together, ratio is 1: 3: 1: 2;
(3) with the SrTiO that makes
3Template and BZT-PT powder are as the powder of preparation casting slurry, add solvent, dispersion agent, binding agent and plastic agent, prepared slurry obtains biscuit through curtain coating, after dry, and the curtain coating biscuit is cut, carries out sintering after lamination, isostatic cool pressing and the plastic removal and obtain piezoceramic material.
3. the method for preparing the low lead piezoelectric ceramics material of high curie point as claimed in claim 2, described solvent is selected ethanol or ethanol and butanone mixed solvent for use; Dispersion agent is selected triolein for use; Binding agent is selected polyvinyl butyral for use; Plastic agent is selected dibutyl phthalate or dibutyl phthalate and polyoxyethylene glycol mixed solution for use.
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|---|---|---|---|
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|---|---|---|---|
| CN 201010563341 CN102060528B (en) | 2010-11-29 | 2010-11-29 | High Curie point and low lead piezoelectric ceramic material and preparation method thereof |
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| CN102060528B CN102060528B (en) | 2013-02-27 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531577A (en) * | 2012-01-04 | 2012-07-04 | 合肥工业大学 | Lead-free piezoelectric material that is CMBZMT and preparation method thereof |
| CN102677173A (en) * | 2012-05-22 | 2012-09-19 | 中国科学院青海盐湖研究所 | Preparation method of lead titanate whiskers |
| CN109553413A (en) * | 2019-01-17 | 2019-04-02 | 南方科技大学 | Textured piezoelectric ceramic and preparation method and application thereof |
| CN113402273A (en) * | 2021-05-31 | 2021-09-17 | 中国科学院上海硅酸盐研究所 | Modified lead titanate-based high-temperature piezoelectric ceramic and preparation method thereof |
| CN113475755A (en) * | 2021-08-06 | 2021-10-08 | 深圳市基克纳科技有限公司 | Heating element and preparation method thereof, atomizer and atomization device |
Citations (2)
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|---|---|---|---|---|
| EP0279133A1 (en) * | 1986-12-19 | 1988-08-24 | Compagnie Europeenne De Composants Electroniques Lcc | Dielectric ceramic compositions having high permittivity |
| CN101429022A (en) * | 2008-12-12 | 2009-05-13 | 同济大学 | Ferro-voltage ceramic component with low sintering temperature character, production and uses thereof |
-
2010
- 2010-11-29 CN CN 201010563341 patent/CN102060528B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0279133A1 (en) * | 1986-12-19 | 1988-08-24 | Compagnie Europeenne De Composants Electroniques Lcc | Dielectric ceramic compositions having high permittivity |
| CN101429022A (en) * | 2008-12-12 | 2009-05-13 | 同济大学 | Ferro-voltage ceramic component with low sintering temperature character, production and uses thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《JOURNAL OF APPLIED PHYSICS》 20090219 Jun Chen et al. Structure and lattice dynamics in PbTiO3-Bi(Zn1/2Ti1/2)O3 solid solutions 第1-5页 1 第105卷, * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531577A (en) * | 2012-01-04 | 2012-07-04 | 合肥工业大学 | Lead-free piezoelectric material that is CMBZMT and preparation method thereof |
| CN102531577B (en) * | 2012-01-04 | 2013-07-31 | 合肥工业大学 | Lead-free piezoelectric material that is CMBZMT and preparation method thereof |
| CN102677173A (en) * | 2012-05-22 | 2012-09-19 | 中国科学院青海盐湖研究所 | Preparation method of lead titanate whiskers |
| CN109553413A (en) * | 2019-01-17 | 2019-04-02 | 南方科技大学 | Textured piezoelectric ceramic and preparation method and application thereof |
| CN109553413B (en) * | 2019-01-17 | 2021-07-16 | 南方科技大学 | Textured piezoelectric ceramic and preparation method and application thereof |
| CN113402273A (en) * | 2021-05-31 | 2021-09-17 | 中国科学院上海硅酸盐研究所 | Modified lead titanate-based high-temperature piezoelectric ceramic and preparation method thereof |
| CN113402273B (en) * | 2021-05-31 | 2022-05-10 | 中国科学院上海硅酸盐研究所 | Modified lead titanate-based high-temperature piezoelectric ceramic and preparation method thereof |
| CN113475755A (en) * | 2021-08-06 | 2021-10-08 | 深圳市基克纳科技有限公司 | Heating element and preparation method thereof, atomizer and atomization device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102060528B (en) | 2013-02-27 |
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